Resist paste



Patented Aug. 8, 1933 UNITEE STATES PATENT OFFICE RESIST PASTE No Drawing. Application October 8, 1931, Serial No. 567,758, and in Germany October 12 Claims.

The present invention relates to resist pastes.

In addition to the so-called resist pastes which contain thickeners such as aqueous starch and/or British gum or gum arabic, if desired together with fillers such as kaolin, zinc oxide or lithopone and the like, and usually contain heavy base metal salts, such as lead and copper salts, as resisting substances, readily soluble sodium salts of nitrated, easily reducible aromatic sulphonic acids have been used together with metal salts such as manganous chloride or a mixture thereof with zinc chloride for some time as resists in dyeing and printing with vat dyestuiis, as is described for example in the German Patents Nos. 196,658, 210,682, 211,526 and 272,685. In these pastes the quantity of the sulphonic acid salts is usually from about to about 16 per cent, that of manganous chloride from about to about 20 per cent and that of zinc chloride from about 15 to about 20 per cent of the whole paste, the remainder up to 100 per cent consisting of the said thickeners which may contain fillers such as kaolin or the like. Nitrobenzene sulphonic acid salts of heavy metals such as copper, lead, tin and manganese have been also employed for the said purpose, but these salts are rather readily soluble and their effect is very low; they overlap on the dyeings when the dyed goods are allowed to stand. Moreover, the copper salts deposit copper on the doctor and render this blunt.

These resists have, however, the following disadvantages: the printing color readily penetrates into the engraving; the white of the resist is tinged pale yellow; when printed goods are allowed to stand after dyeing the resist readily overlaps on to the dyeing and causes discolored patches which can only be removed again by a reducing bath; when large amounts of goods are dyed the vat is oxidized and partly destroyed by the nitro compound which has been dissolved out, and the like. When employing a slight excess of these resists, moreover, halos and the formation of the so-called burring are obtained.

We have now found that the said disadvantages no longer arise, or only arise to an inconsiderable extent by employing the difiicultly water-soluble alkaline earth metal salts, including magnesium salts, of the sulphonic acids of readily reducible aromatic nitro compounds instead of the readily soluble alkali metal salts. Aromatic easily reducible nitrosulphonic acid salts suitable for the purposes according to the present invention are for example the isomeric sulphonic acids of nitrobenzene, nitrotoluene, nitrochlorbenzene, dinitrochlorbenzene, nitro-amino-phenol, nitrobenzaldehyde, di-nitrophenol, di-nitronaphthalene, nitrotetrahydronaphthalene, di-nitrodiphenyl or dinitrostilbene which give dimcultly water-soluble alkaline earth metal salts. Specific examples of the said sulphonic acids are 1.3-nitrobenzene sulphonic acid, 4-nitro-chlorbenzene-2-sulphonic acid, 4-nitro-2-amino-phenol-6-sulphonic acid, 2.6-di-nitrophenol--sulphonic acid, 2-nitroben zaldehyde--sulphonic acid, 2.2-di-nitrodiphenyl-4.4'-di-sulphonic acid, 4.4-di-nitrostilbene di-sulphonic acid, 1.5-dinitronaphthalene monosulphonic acids, and 2A-di-nitro-chlorbenzene-6- sulphonic acid.

The quantities employed of the sulphonic acid salts are about the same as hitherto employed of the water-soluble salts. The water-insoluble 'sul-- phonic acid salts give the particular advantage of dispensing with the addition of metal salts, at least of zinc chloride, which may be replaced by an equivalent quantity of thickener. Zinc chloride may be employed, however, together with manganous chloride, if so desired. The said compounds may be employed for white resists and for color resists.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples; The parts are by weight.

Example 1 180 parts of kaolin and parts of the barium salt of meta-nitrobenzene sulphonic acid (or the corresponding toluene or xylene derivatives) are made into a paste with 280 parts of water, 145 parts of British gum dispersed in 145 parts of water are added and 200 parts of manganous chloride are dissolved therein. The paste obtained is printed onto white goods of vegetable origin, such as cotton, linen or artificial silk, and

the goods are then dyed with any vat dyestuff such as those referred to in Schultz, Farbstofftabellen, 1923 ed. under Nos. 760, 763 or 767, from a hydrosulphite-glucose vat in the usual manner. After acidification and washing an excellent dazzling white resist is obtained.

Example 2 from a hydrosulphite-glucose vat in the usual manner. After acidification and washing a dazzling white resist is obtained in the violet dyeing. 1.5 dinitronaphthalene mono sulphonic acid calcium salt may be employedin the same manner.

Example 3 parts of Indanthren Brilliant green B (Schultz, Farbstofitabellen 1931, vol. 1, No. 1269, 20 per cent aqueous paste) 100 parts ofkaolin and parts of the barium salt of meta-nitrobenzene sulphonic acid are made into a paste with parts of water, 255 parts of gum arabic dispersed in 260 parts of water are added and 150 parts of potash and 100 parts of sodium formaldehyde sulphoxylate are dissolved therein. The said paste is printed onto white goods and the goods are steamed for 5 minutes in a rapid steamer and dyed in the usual manner from a hydrosulphite-glucose vat. Vigorous green resist ehects are obtained.

Example 4 75 parts of the barium salt of 2.6-dinitrochlorbenzenei-sulphonic'acid (or of the barium salt of 2.4-di-nitrochlorbenzene-6-sulphonic acid) and 100 parts of kaolin are made into a paste with 100 parts of water, stirred with 575 parts of thickening and then 150 parts of manganous chloride are dissolved therein. The said printing color is printed on to white goods which are then dyed with any vat dyestuff, such as those referred to in Schultz, Farbstofitabellen, 1923 ed. under Nos.

1 760, 763 or 767, in the usual manner in a hydrosulphite glucose vat. Dazzling White resists are obtained.

Example 5 Cotton piece goods are primed with a solution of 20 parts of 2.3-hydroxynaphthoic acid anilide, 20 parts of an aqueous caustic soda solution of 34 B. strength and 50 parts of Turkey red oil made up to 1 liter, are then printed with a printing color of 50 parts of kaolin, 200 parts of gum arabic l: 1, 50 parts of the barium salt of metanitrobenzene sulphonic acid, 175 parts of vegetable gum dissolved in 175 parts of water, 100 parts of manganous chloride, 80 parts of the sodium salt of the nitrosamine of meta-nitroorthoanisidine and 45 parts of water and then dyed in the usual manner from a hydrosulphiteglucose vat with Indanthren blue RS double paste (Schultz, Farbstofitabellen 1923, vol. 1, No. 838) (30 grams per liter). The cotton piece goods are acidified, and washed, and a vigorous red resist in the blue dyeing is obtained.

What we claim is:-

1. As a new composition, a resist paste comprising a thickener and an alkaline earth metal salt of a readily reducible aromatic nitro-sulphonic acid.

2. As a new composition, a resist paste comprising a thickener, a filler and an alkaline earth metal salt of a readily reducible aromatic nitrosulphonic acid.

3. As a new composition, a resist paste comprising a thickener and from about 5 to 10 per cent, by weight of the whole paste, of an alkaline earth metal salt of a readily reducible aromatic nitro-sulphonic acid.

4. As a new composition, a metal resist paste comprising a thickener, manganous chloride and an alkaline earth metal salt of a readily reducible aromatic nitro-sulphonic acid.

5. As a new composition, "a resist paste comprising a thickener and an alkaline earth metal salt of a nitrobenzene sulphonic acid.

6. As a new composition, a resist paste comprising a thickener and a barium salt of a readily reducible aromatic nitro-sulphonic acid.

7. As a new composition, a resist paste comprising a thickener and a barium salt of a nitrobenzene sulphonic acid.

8. As a new composition, a metal resist paste comprising a thickener, manganous chloride and an alkaline earth metal salt of a nitrobenzene A sulphonic acid.

9. As a new composition, a metal resist paste comprising a thickener, manganous chloride and a barium salt of a nitrobenzene sulphonic acid. 10. As a new composition, a color resist paste comprising a thickener, a vat dyestulf and an alkaline earth metal salt of a readily reducible, aromatic nitro-sulphonic acid.

11. As a new composition, a color resist paste comprising a thickener, a vat dyestufi and a 

